Moldable poly(arylene ether) thermosetting compositions, methods, and articles

ABSTRACT

A moldable thermosetting composition comprises a poly(arylene ether), a thermosetting resin, a toughening agent, and an amine cure agent. The compositions may be conveniently prepared without solvents, and the poly(arylene ether) may be provided in the form of an easily dissolved solid concentrate with the thermosetting resin.

BACKGROUND OF INVENTION

[0001] Curable resin compositions comprising thermosetting resins andpoly(arylene ether) resins are known. However, it has been difficult toprepare thermosetting compositions comprising substantial amounts ofhigher molecular weight poly(arylene ether)s, for example, those havingintrinsic viscosities of about 0.30 dL/g or greater (as measured at 25°C. in chloroform). As described, for example, in U.S. Pat. No. 4,912,172to Haligren et al., high temperatures are typically required to dissolvethe poly(arylene ether)s in the thermosetting resin. High temperature,latent catalysts such as aluminum tris(acetylacetonate) can then bedissolved into the solution to initiate curing. However, the hightemperatures required to prevent the poly(arylene ether) fromprecipitating out of solution are incompatible with the use of many cureagents, particularly amine cure agents, which would undergo a rapid anduncontrolled reaction at such elevated temperatures.

[0002] U.S. Pat. No. 4,623,558 to Lin describes a plastisol dispersioncomposition comprising (1) poly(phenylene oxide) in powder form, whichis insoluble in the reactive plasticizer at room temperature andplasticizable at a temperature at or above the fluxing temperature; (2)a liquid reactive plasticizer member of the group consisting of (a) atleast one epoxide resin having an average of more than one epoxide groupin the molecule, (b) at least one liquid monomer, oligomer or prepolymercontaining at least one ethylenically unsaturated group and (c) amixture of (a) and (b); said liquid reactive plasticizer being capableof solvating the poly (phenylene oxide) at the fluxing temperature andbeing present in an amount ranging from 5 to 2,000 parts per 100 partsby weight of (1); and (3) 0.01 to 10% by weight of (2) of a latentcuring agent, such as a thermal initiator or photoinitiator, forplasticizers present in the composition. The latent curing agents arenot reactive with the thermoset resins at lower temperatures.

[0003] There remains a need for curable poly(arylene ether)-containingresin compositions that allow the poly(arylene ether) to remain in aworkable state in the thermosetting resin at a temperature suitable foraddition of a low-temperature cure agent. There also remains a need forcurable poly(arylene ether)-containing resin compositions that formhomogeneous solutions at lower temperature for intimate mixing of thepoly(arylene ether) into the resin matrix.

SUMMARY OF INVENTION

[0004] One embodiment is a curable resin composition comprising: about 5to about 50 parts by weight of a poly(arylene ether); about 25 to 90parts by weight of a thermosetting resin selected from the groupconsisting of epoxy resins, polyester resins, polyimide resins,bis-maleimide resins, cyanate ester resins, vinyl resins, benzoxazineresins, benzocyclobutene resins, and mixtures comprising at least one ofthe foregoing thermosetting resins; about 0.5 to about 15 parts byweight a compatibilizing agent selected from the group consisting ofpolyvinyl acetal resins, styrene-butadiene-styrene (SBS) blockcopolymers, styrene ethylene styrene (SES) block copolymers,styrene-ethylene-butylene-styrene (SEBS) block copolymers,functionalized butadiene-acrylonitrile copolymers, styrene-butadienecore shell rubbers, styrene-butadiene-styrene core shell rubbers, andmixtures comprising at least one of the foregoing compatibilizingagents; and about 3 to about 150 parts by weight per 100 parts of weightof the thermosetting resin of an amine cure agent selected from thegroup consisting of amidoamines, polyamides, cycloaliphatic amines,modified cycloaliphatic amines, aromatic amines, modified aromaticamines, BF₃-amine adducts, imidazoles, guanidines, arylene polyamines,and mixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to 100.

[0005] Another embodiment is a cured resin composition comprising thereaction product of the above curable resin composition.

[0006] Another embodiment is an article comprising the above cured resincomposition.

[0007] Another embodiment is a method of preparing a curable resincomposition, comprising: forming an intimate blend comprising about 5 toabout 50 parts by weight of a poly(arylene ether); about 25 to 90 partsby weight of a thermosetting resin selected from the group consisting ofepoxy resins, polyester resins, polyimide resins, bis-maleimide resins,cyanate ester resins, vinyl resins, benzoxazine resins, benzocyclobuteneresins, and mixtures comprising at least one of the foregoingthermosetting resins; about 0.5 to about 15 parts by weight of acompatibilizing agent selected from the group consisting of polyvinylacetal resins, styrene-butadiene-styrene block copolymers,styrene-ethylene-styrene block copolymers,styrene-ethylene-butylene-styrene block copolymers, functionalizedbutadiene-acrylonitrile copolymers, styrene-butadiene core shellrubbers, styrene-butadiene-styrene core shell rubbers, and mixturescomprising at least one of the foregoing compatibilizing agents; andabout 3 to about 150 parts by weight per 100 parts by weightthermosetting resin of an amine cure agent selected from the groupconsisting of amidoamines, polyamides, cycloaliphatic amines, modifiedcycloaliphatic amines, aromatic amines, modified aromatic amines,BF₃-amine adducts, imidazoles, guanidines, arylene polyamines, andmixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to 100.

[0008] Another embodiment is a method of preparing a poly(aryleneether)-containing solid concentrate, comprising: blending about 30 toabout 90 parts by weight of a poly(arylene ether) and about 10 to about70 parts by weight of a thermosetting resin in the presence of asuitable solvent to form a homogeneous solution; and substantiallyremoving the suitable solvent to yield a solid concentrate; wherein theparts by weight of the poly(arylene ether) and the thermosetting resinsum to 100.

[0009] Another embodiment is a poly(arylene ether)-containing solidconcentrate prepared according to the above method.

DETAILED DESCRIPTION

[0010] One embodiment is a curable resin composition comprising: about 5to about 50 parts by weight of a poly(arylene ether); about 25 to 90parts by weight per 100 parts by weight of a thermosetting resinselected from the group consisting of epoxy resins, polyester resins,polyimide resins, bis-maleimide resins, cyanate ester resins, vinylresins, benzoxazine resins, benzocyclobutene resins, and mixturescomprising at least one of the foregoing thermosetting resins; about 0.5to about 15 parts by weight per 100 parts by weight of a compatibilizingagent selected from the group consisting of polyvinyl acetal resins,styrene-butadiene-styrene (SBS) block copolymers, styrene ethylenestyrene (SES) block copolymers, styrene-ethylene-butylene-styrene (SEBS)block copolymers, functionalized butadiene-acrylonitrile copolymers,styrene-butadiene core shell rubbers, styrene-butadiene-styrene coreshell rubbers, and mixtures comprising at least one of the foregoingcompatibilizing agents; and about 3 to about 150 parts by weight per 100parts of weight of the thermosetting resin of an amine cure agentselected from the group consisting of amidoamines, polyamides,cycloaliphatic amines, modified cycloaliphatic amines, aromatic amines,modified aromatic amines, BF₃-amine adducts, imidazoles, guanidines,arylene polyamines, and mixtures comprising at least one of theforegoing amine cure agents; wherein the parts by weight of thepoly(arylene ether), the thermosetting resin, and the compatibilizingagent sum to 100.

[0011] It has unexpectedly been discovered that the use of thecompatibilizing agent in the above composition allows the poly(aryleneether) to remain finely dispersed in the thermosetting resin attemperatures suitable for the use of amine cure agents. While notwishing to be bound by any particular hypothesis, the present inventorsbelieve that their invention may function as follows. The thermosettingresin may act as a solvent for the poly(arylene ether), dissolving it toform a homogeneous solution at elevated temperature. In the absence ofthe compatibilizing agent, cooling of the solution leads toprecipitation of the poly(arylene ether) in large, non-homogeneous solidaggregates, including crystalline portions in some cases, forming anintermediate composition unsuitable for further addition of catalysts orhardeners. Addition of the compatibilizing agents prior to cooling thesolution appears to inhibit crystallization and formation of intractableaggregates, and it allows formation of a finely divided dispersion thatis workable at temperatures suitable for the use of amine curing agents.

[0012] In addition, it has been discovered that the compatibilizingagent may be used to prepare poly(arylene ether)-containing solidconcentrates. For example, a solvent such as toluene may be used to forma solution containing the poly(arylene ether), the compatibilizingagent, and the thermosetting resin. Removal of solvent from thissolution creates a solid concentrate in the form of a stable powder thatmay be dissolved readily into additional thermoset resin, catalyzed, andcured. It has been possible to prepare solid concentrates with a widerange of poly(arylene ether) concentrations for maximum flexibility informulating. For example, concentrates having high concentrations ofpoly(arylene ether) may be diluted with additional thermosetting resin,and concentrates having lower concentrations of poly(arylene ether) maybe melted and used directly.

[0013] Suitable poly(arylene ether) resins comprise a plurality ofstructural units of the formula

[0014] wherein for each structural unit, each Q¹ is independentlyhalogen, primary or secondary C₁-C₇ alkyl, phenyl, C₁-C₇ haloalkyl,C₁-C₇ aminoalkyl, C₁-C₇ hydrocarbonoxy, or C₂-C₇ halohydrocarbonoxywherein at least two carbon atoms separate the halogen and oxygen atoms;and each Q² is independently hydrogen, halogen, primary or secondaryC₁-C₇ alkyl, phenyl, C₁-C₇ haloalkyl, C₁-C₇ aminoalkyl, C₁-C₇hydrocarbonoxy, or C₂-C₇ halohydrocarbonoxy wherein at least two carbonatoms separate the halogen and oxygen atoms. Examples of suitableprimary C₁-C₇ alkyl groups are methyl, ethyl, n-propyl, n-butyl,isobutyl, n-pently, isopentyl, 2-methylbutyl, n-hexyl,2,3-dimethylbutyl, 2-, 3-, or 4-methylpentyl, and the correspondingheptyl groups. Examples of secondary C₁-C₇ alkyl groups are isopropyl,sec-butyl and 3-pentyl. Preferably, any alkyl radicals are straightchain rather than branched. Preferably, each Q¹ is C₁-C₇ alkyl orphenyl, especially C—C alkyl, and each Q² is hydrogen.

[0015] Both homopolymer and copolymer poly(arylene ether) polymers areincluded. The preferred homopolymers are those containing2,6-dimethylphenylene ether units. Suitable copolymers include randomcopolymers containing, for example, such units in combination with2,3,6-trimethyl-1,4-phenylene ether units or copolymers derived fromcopolymerization of 2,6-dimethylphenol with 2,3,6-trimethylphenol. Alsoincluded are poly(arylene ether) polymers containing moieties preparedby grafting vinyl monomers or polymers such as poly(styrene), as well ascoupled poly(arylene ether) polymers in which coupling agents such aslow molecular weight polycarbonates, quinones, heterocycles and formalsundergo reaction in a known manner with the hydroxy groups of twopoly(arylene ether) chains to produce a higher molecular weight polymer.Poly(arylene ether) polymers of the composition further includecombinations of any of the above. Many suitable random copolymers, aswell as homopolymers, are disclosed in the patent literature. Referenceis made to U.S. Pat. Nos. 4,054,553 to Olander, 4,092,294 to Bennett,Jr. et al., 4,477,649 to Mobley, 4,477,651 to White et al., and4,517,341 to White.

[0016] The poly(arylene ether) resin is typically prepared by theoxidative coupling of at least one monohydroxyaromatic compound such as2,6-xylenol or 2,3,6-trimethylphenol. Catalyst systems are generallyemployed for such coupling; they typically contain at least one heavymetal compound such as a copper, manganese or cobalt compound, usuallyin combination with various other materials.

[0017] Particularly useful poly(arylene ether) resins are those havingterminal hydroxy groups and a number average molecular weight of about8,000 to about 13,000 atomic mass units (amu), preferably about 9,000 toabout 12,000 amu, more preferably about 10,000 to about 11,000 amu, asdetermined by gel permeation chromatography using polystyrene standards.The poly(arylene ether) resin accordingly may have an intrinsicviscosity (I.V.) of about 0.20 to about 0.40 deciliters per gram (dL/g),preferably about 0.25 to about 0.35 dL/g, more preferably about 0.28 toabout 0.32 dL/g, as measured in chloroform at 25° C. Such poly(aryleneether)s may be synthesized directly or obtained by subjectingpoly(arylene ether)s to redistribution. Suitable methods forredistribution are described in, for example, U.S. Pat. No. 5,834,565.In one procedure, low molecular weight poly(arylene ether)s are preparedfrom poly(arylene ether)s typically having a number average molecularweight of about 15,000 to 25,000 amu. Such preparation of a lowmolecular weight poly(arylene ether) resin can be accomplished byreacting the poly(arylene ether) resin with an oxidizing agent such as aperoxide or a quinone, with or without a phenol. Another procedure is toobtain a low molecular weight poly(arylene ether) resin by oxidativecoupling as described above to produce resins of the desired numberaverage molecular weight which is isolated, preferably, by a directisolation method. However, even such low molecular weight resins canoptionally be functionalized with a peroxide or peroxide and a phenol toachieve even lower molecular weight.

[0018] Phenolics useful in the redistribution reaction described hereininclude all known phenol compounds, including those having the formula

[0019] wherein A¹ is any aromatic, mixed aliphatic aromatic hydrocarbon,heterocycle or derivative of the like, —OH is a hydroxy residue, and nis an integer from 1 to about 10, preferably from 1 to about 5. Aparticularly preferred phenolic is 2,2-bis(4-hydroxyphenyl)propane.

[0020] In general, any peroxide would be useful in the redistributionreaction, including those having the formula A²—O—O—A³ wherein A² and A³are any aliphatic acyl, aromatic acyl group, alkyl, or mixed aliphaticaromatic hydrocarbon, hydrogen or inorganic ester moiety or derivativesof the like. Typical peroxides include without limitation: 1) diacylperoxides such as dibenzoyl peroxide, 4,4′-di-t-butylbenzoyl peroxide orother aryl substituted derivatives, dilauryl peroxide, acetyl benzoylperoxide, acetyl cyclohexylsulfonyl peroxide and diphthaloyl peroxide;2) peroxydicarbonates such as dicetylperoxydicarbonate; 3) peroxyacidssuch as perbenzoic acid, 3-chloroperbenzoic acid, 4-nitroperbenzoicacid, and other substituted derivatives of perbenzoic acid, peroxyaceticacid, peroxypropanoicacid, peroxybutanoic acid, peroxynonanoic acid,peroxydodecanoic acid, diperoxyglutaric acid, diperoxyadipic acid,diperoxyoctanedioic acid, diperoxynonanedioic acid, diperoxydecanedioicacid, diperoxydoecandioic acid, monoperoxyphthalic acid, as well as theinorganic acids such as peroxysulfuric acid, peroxydisulfuric acid,peroxyphosphoric acid, peroxydiphosphoric acid and their correspondingsalts; and 4) peroxycarboxylic esters such as t-butyl performate,t-butyl peracetate, t-butyl peroxyisobutyrate, t-butyl perbenzoate,cumyl perbenzoate, t-butyl peroxynonanoate, t-butyl monoperoxymaleate,t-butyl monoperoxyphthalate, di-t-butyl diperoxyadipates, and2,5-dimethyl 2,5-bis(benzoylperoxy)hexane.

[0021] These peroxides may be used alone or in combination with orwithout the presence of a catalyst to induce decomposition of theperoxide and increase the rate of radical production. Other oxidizingagents known in the art include quinones such as 2,2′,6,6′-tetramethyldiphenoquinone (TMDQ) may also be used in the presence or absence of aphenol.

[0022] The composition may comprise the poly(arylene ether) in an amountof about 5 to about 50 parts by weight per 100 parts by weight total ofthe poly(arylene ether), the thermosetting resin, and thecompatibilizing agent. Within this range, it may be preferred to use atleast about 10 parts by weight, more preferably at least about 15 partsby weight, of the poly(arylene ether). Also within this range, it may bepreferred to use up to about 40 parts by weight, more preferably up toabout 30 parts by weight, of the poly(arylene ether).

[0023] The curable composition further comprises a thermosetting resinselected from epoxy resins, polyester resins, polyimide resins,bis-maleimide resins, cyanate ester resins, vinyl resins, benzoxazineresins, benzocyclobutene resins, mixtures comprising at least one of theforegoing thermosetting resins, and the like. The thermosetting resinmay be present in its monomeric, oligomeric, or polymeric state and mayfurther include reaction products with art-known cure agents andcatalysts.

[0024] The epoxy resin useful in this invention would include, in itsbroadest sense, any epoxy compound. Suitable epoxy compounds useful inthis formulation may have the formula

[0025] wherein A⁴ is any aromatic, aliphatic, mixed aliphatic aromatichydrocarbon, heterocycle or derivative of the like; X is an epoxycontaining residue; and p is any integer, preferably from 1 to about100, more preferably 2 to about 100.

[0026] When flame retardance is required, it is preferred that theepoxide comprise at least two epoxy compounds, one being brominated toprovide flame retardancy and the other at levels sufficient to provide atotal bromine content of about 10 to about 30 weight percent, based onthe weight of the solid composition. Preferred epoxy compounds includethose wherein p is 1 to 4, more preferably those wherein p is 2.

[0027] Typical to this family of materials are:

[0028] 1) Diepoxides having the formula

[0029] wherein A⁵ and A⁶ are aromatic radicals, Y is a single bond or adivalent radical, and q is an integer from 0 to about 500. The radicalsA⁵ and A⁶ may be substituted or unsubstituted with typical groups chosenfrom aryl, alkyl, alkoxy, halogen, and the like. Y may include divalentradicals such as alkylene, cycloalkylene, arylene, oxy, thio, sulfonyl,sulfoxy, and carbonyl.

[0030] Common examples of the above diepoxide compounds includediglycidyl ethers often produced by the condensation of epichlorohydrinwith a bisphenol where q=0. Typical of this class of compounds are thediglycidyl ethers of 4,4′-(1-methylethylidene) diphenol, 4,4′-(1-methylethylidene)bis(2-methylphenol),4,4′-(1-methylethylidene)bis(2,6-dimethylphenol),4,4′-(1,1-cyclopentylidene)diphenol, 4,4′-(cyclohexylidene)diphenol,4,4′-(1-methylethylidene)bis(2,6-dibromo phenol),4,4′-methylenediphenol, 4,4′-(1-methylethylidene)bis(2-allylphenol),4,4′-(1-methylethylidene)bis(2-t-butyl-5-methylphenol),4,4′-(1-methylethylidene)bis(2-t-butyl-5-methylphenol),4,4′-(1-methylpropylidene)bis(2-t-butyl-5-ethylphenol),4,4′-(1,4-bis(methylethylidene)phenyl)bis (2-t-butyl-5-methylphenol),4,4′-biphenol, hydroquinone, resorcinol, and the like. Oligomericproducts generated during this condensation reaction are also known andare useful. Such compounds are exemplified by the oligomericcondensation product of bisphenol A and epichlorohydrin sold by ShellCorporation under the tradename EPON® as EPON® 825 (q=0) and EPON® 828(q=0.14)

[0031] 2) The reaction products of the above diepoxides with bisphenols,commonly referred to as upstaged resins. A typical example includes thecondensation product of bisphenol A diglycidyl ether withtetrabromobisphenol A. The partial condensation products suitable foruse may be prepared by heating the mixture of compounds, as hereinabovedescribed, at a temperature in the range of about 50° C. to about 225°C., preferably about 70° C. to about 200° C., more preferably about 100°C. to about 190° C., in the presence of a catalytic amount of at leastone basic reagent, such as copper (for instance lithiumdimethylcuprate), amine, phosphine, or metal salt with a strong alkoxidecounter ion.

[0032] The triarylphosphines, especially triphenylphosphine, are thepreferred basic reagents for the bisphenol bisepoxide condensationreaction for their effectiveness at low levels, their low tendency tocause side reactions, and their harmlessness when they remain presentafter the reaction is complete. They are usually employed in the amountof about 0.1% to about 0.5% by weight. The reaction is preferablyconducted in an inert atmosphere such as nitrogen, especially when atriarylphosphine is employed as a catalyst.

[0033] 3) Multifunctional epoxides as described by the formula

[0034] wherein Y is as defined above; A⁷ and A⁸ are aromatic radicalseither substituted or unsubstituted with typical substituting groupschosen from aryl, alkyl, alkoxy, halo, and the like; and r is an integerfrom 0 to about 500. The materials described by this formula include allepoxidized phenolic resins including epoxidized novolacs and resols.Most common examples of compounds described by this formula includeglycidyl ethers produced by the condensation of epichlorohydrin with aphenolic resin. Examples of this class of compounds include the glycidylethers of phenol formaldehyde novolac, cresol formaldehyde novolac,bromophenol formaldehyde novolac, t-butylphenol formaldehyde novolac,phenolic resins derived from the condensation of phenol with a diene ormixtures of dienes, such as dicyclopentadiene or butadiene, oradditionally, with a polybutadiene resin.

[0035] Other multifunctional epoxides include phloroglucinol triglycidylether and tetrakis(glycidoxyphenyl) ethane.

[0036] 4) Glycidyl ethers of amines, amides, or nitrogen containingheterocycles. These materials may include triglycidylcyanurate,triglycidylisocyanurate, N,N,N′N′-tetraglicidyldiaminodiphenylmethane,N,N,—O—triglycidyl-4-aminophenol, N,N-diglycidyl aniline, andN,N-diglycidyl hydantoin.

[0037] 5) Glycidyl ethers of carboxylic acids such as diglycidylphthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalateand diglycidyl adipate.

[0038] 6) Homopolymers or copolymers prepared from unsaturated epoxidessuch as glycidyl acrylate, glycidyl methacrylate and allyl glycidylether. As mentioned, these materials may be used as homopolymers orcopolymers obtained from mixtures of the unsaturated epoxides mentionedabove or mixtures of unsaturated epoxides and other vinyl monomers knownin the practice of vinyl polymerization.

[0039] 7) Polysiloxanes containing epoxy functionality such as theglycidyl ether of 1,3-bis(3-hydroxypropyl)tetramethyldisiloxane.

[0040] 8) Compounds prepared by epoxidation of alkenes, dienes orpolyenes, such as phenylglycidyl ether, allylglycidyl ether,napthylglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, and substituted derivativesthereof. In addition, epoxidized polyenes such as polybutadiene resinsor butadiene containing copolymers would be useful.

[0041] In one embodiment, the thermosetting resin may comprise anepoxy-functionalized dihydric phenol, such as bisphenol polyglycidylethers derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) or bis(2-hydroxyphenyl)methane (bisphenol F).

[0042] Other useful thermosetting components comprise vinylic compounds,including triallylisocyanurate, triallylcyanurate, diallyl phthalate,diallyl isophthalate, diallyl maleate, diallyl fumarate, diethyleneglycol diallylcarbonate, triallyl phosphate, ethylene glycol diallylether, allyl ethers of trimethylolopropane, partial allyl ethers ofpentaerythritol, diallyl sebacate, allylated novolacs, allylated resolresins, and/or cyanate esters. These various thermosetting resins can beused either individually or in combination with one another. Examples ofvinyl thermosetting resins include those known in the art, such as thosedescribed in S. H. Goodman, “Handbook of Thermoset Plastics”, NoyesPublications (1986).

[0043] Cyanate esters include those having the formula

[0044] wherein A⁹ is any aromatic, aliphatic, mixed aliphatic aromatichydrocarbons, heterocycles or derivatives of the like, X is a cyanategroup, and s is an integer from 1 to 10 and preferably from 1 to 4.Typical of this class of compounds are those derived from the reactionof cyanogen halides with the bisphenols described above. Variousexamples of cyanate esters can be found in 1. Hamerton, “Chemistry andTechnology of the Cyanate Esters”, Chapman Hall (1994).

[0045] Polyimides, including bismaleimides, include those known in theart, such as those described in D. Wilson, H. D. Stenzenberger and P. M.Hergenrother, “Polyimides”, Chapman Hall (1990).

[0046] Benzoxazines include those known to the art, such as thosedescribed in U.S. Pat. No. 5,973,144 to Ishida.

[0047] The composition may comprise the thermosetting resin in an amountof about 25 to about 90 parts by weight per 100 parts by weight total ofthe poly(arylene ether), the thermosetting resin, and thecompatibilizing agent. Within this range, it may be preferred to use atleast about 50 parts by weight, more preferably at least about 60 partsby weight, of the thermosetting resin. Also within this range, it may bepreferred to use up to about 85 parts by weight of the thermosettingresin.

[0048] The composition further comprises a compatibilizing agent to keeppoly(arylene ether) in a fine, dispersed, and workable state.Compatibility is meant to include the stabilization of the compositionagainst gross phase separation. Indicators of improved compatibilizationinclude, for example, increased ductility and improved phase morphologystabilization. Improved compatibility of the blend componentscontributes to the desirable physical properties of the curable resincomposition.

[0049] Preferred compatibilizing agents include polyvinyl acetal resins,including copolymers of polyvinyl butyral and other vinyl monomers suchas vinyl acetate, and partially hydrolyzed derivatives therefrom. Theterm “polyvinyl butyral” encompasses such copolymers. An example of sucha polyvinyl butyral is poly(vinyl butyral-co-polyvinylalcohol-co-polyvinyl acetate). Of particular utility is a polyvinylbutyral resin of molecular weight 50,000 to 120,000, available fromSolutia under the trademark BUTVAR®. Other compatibilizing agentsinclude, for example, low molecular weight thermoplastic elastomersknown in the art, such as styrene-butadiene-styrene (SBS) blockcopolymers, styrene-ethylene-styrene (SES) block copolymers,styrene-ethylene-butylene-styrene (SEBS) block copolymers andfunctionalized butadiene-acrylonitrile copolymers such as those soldunder the tradename HYCAR® Reactive Liquid Rubbers by B. F. GoodrichCompany. Also included are core shell type toughening agents such asstyrene-butadiene and styrene-butadiene-styrene core shell rubbers.Other useful materials may be found in W. Hofmann and C. Hanser, “RubberTechnology Handbook”, Verlag Publishers (1989); and B. Ellis, “Chemistryand Technology of the Epoxy Resins”, Chapman Hall (1993).

[0050] The composition may comprise the compatibilizing agent in anamount of about 0.5 to about 15 parts by weight per 100 parts by weighttotal of the poly(arylene ether), the thermosetting resin, and thecompatibilizing agent. Within this range, it may be preferred to use atleast about 2 parts by weight, more preferably at least about 3 parts byweight, of the compatibilizing agent. Also within this range, it may bepreferred to use up to about 10 parts by weight, more preferably up toabout 8 parts by weight, of the compatibilizing agent.

[0051] The composition further comprises a cure agent to effectcrosslinking between the reactive thermosetting components. For thepurpose of this invention, the term cure agent is meant to includecuring catalysts and co-catalysts. Any known cure agent suitable for thedesired application may be employed. Suitable cure agents are described,for example, in B. Ellis, “Chemistry and Technology of the EpoxyResins”, Chapman Hall (1993).

[0052] Preferred cure agents include amine cure agents, such asamidoamines, polyamides, cycloaliphatic amines, modified cycloaliphaticamines, aromatic amines, modified aromatic amines, BF₃-amine adducts,imidazoles, guanidines, arylene polyamines, mixtures comprising at leastone of the foregoing amine cure agents, and the like.

[0053] Particularly useful imidazoles are imidazole,1,2-dimethylimidazole, 2-methylimidazole, 2-heptadecylimidazole and1-(2-cyanoethyl)-2-phenylimidazole.

[0054] Suitable guanidines may be represented by the formula

[0055] wherein Z¹ and Z³ independently represent a C₁-C₄ alkyl group,and Z², Z⁴ and Z⁵ independently represent hydrogen or a C—C alkyl group.

[0056] Particularly useful cure agents include arylene polyamines withalkyl substitution on the aromatic ring. Highly preferred cure agentsinclude 4,4′-methylenebis[2,6-diethylaniline](MDEA), anddiethyltoluenediamine (DETDA).

[0057] Examples of cure agents further include metal carboxylateswherein the metal is zinc, magnesium or aluminum, and the carboxylate isa C₁₋₂₄ carboxylate such as acetate, octoate, or stearate. Othersuitable cure agents include aluminum and zinc salts of diketones of theformula

[0058] wherein each of R¹ and R² is a C alkyl or aryl and R is hydrogenor C₁-C₂₀ alkyl or aryl; preferably, R¹ and R² are methyl, and R³ ishydrogen.

[0059] The amount of cure agent employed may vary according to the cureagent equivalent weight and the thermosetting resin type and amount. Thecomposition may typically comprise the cure agent in an amount of about3 to about 150 parts by weight per 100 parts by weight of thethermosetting resin. Within this range, it may be preferred to use atleast about 20 parts by weight, more preferably at least about 30 partsby weight, of the cure agent. Also within this range, it may bepreferred to use up to about 100 parts by weight, more preferably toabout 60 parts by weight, of the cure agent.

[0060] The curable resin composition may, optionally, further comprise aplasticizer to reduce the brittleness of cured substrates. When used inappropriate quantities, these plasticizers reduce the glass transitiontemperature of the poly(arylene ether) less than 1° C. per partpoly(arylene ether) without severely affecting the glass transitiontemperature of the remaining thermosetting components. Suitableplasticizers are known and include, for example, resorcinol diphosphate,bisphenol-A-diphosphate and isopropylated phenol phosphate. Whenpresent, the plasticizer may be used at about 0.1 to about 20 parts byweight per 100 parts by weight of the poly(arylene ether). Within thisrange, it may be preferred to use at least about 0.5 part by weight,more preferably at least about 1 part by weight, of the plasticizer.Also within this range, it may be preferred to use up to about 10 partsby weight, more preferably up to about 3 parts by weight, of theplasticizer.

[0061] The curable resin composition may further optionally comprisevarious additives, for example, antioxidants, UV absorbers, stabilizerssuch as light stabilizers and others, lubricants, pigments, dyes,colorants, anti-static agents, flame retardants, impact modifiers, moldrelease agents, and the like, and mixtures thereof. Selection of typesand amounts of such additives may be performed without undueexperimentation by those skilled in the art. Exemplary antioxidantsinclude organophosphites, for example, tris(nonyl-phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,2,4-di-tert-butylphenyl phosphite, or distearyl pentaerythritoldiphosphite; alkylated monophenols, polyphenols and alkylated reactionproducts of polyphenols with dienes, such as, for example,tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methaneand 3,5-di-tert-butyl-4-hydroxyhydrocinnamate octadecyl; butylatedreaction products of para-cresol and dicyclopentadiene; alkylatedhydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols;benzyl compounds; esters ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydricor polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds, such as, for example, distearylthiopropionate,dilaurylthiopropionate, ditridecylthiodipropionate; and amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

[0062] Flame retardant additives include both reactive and non-reactiveflame retardant additives such as tetrabromobisphenol A derivatives,including the bis(2-hydroxyethyl)ether of tetrabromobisphenol A, thebis(3-acryloyloxy-2-hydroxypropyl) ether of tetrabromobisphenol A, thebis(3-methacryloyloxy-2-hydroxypropyl) ether of tetrabromobisphenol A,the bis(3-hydroxypropyl) ether of tetrabromobisphenol A, thebis(2,3-dibromopropyl) ether of tetrabromobisphenol A, the diallyl etherof tetrabromobisphenol A, and the bis(vinylbenzyl) ether oftetrabromobisphenol A; pentabromobenzyl acrylate; dibromostyrenes;tribromostyrenes; tetrabromocyclooctanes;dibromoethyldibromocyclohexanes such as1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane;ethylene-bis-tetrabromophthalimide; hexabromocyclododecanes;tetrabromophthalic anhydrides; brominated diphenylethers such asdecabromodiphenyl ether; poly(2,6-dibromophenylene ether); andtris(2,4,6-tribromophenoxy-1,3,5-triazine; as well asphosphorus-containing additives, for example, the phosphorus-containingadditives described above and those described in R. Gachter and H.Muller (eds.), P. P. Klemchuck (assoc. ed.), “Plastic AdditivesHandbook, 4^(th) Edition”, Hansen Publishers, (1993). Such additives aretypically used in concentrations of about 12 to about 20 weight percentof the brominated additive, or about 15 to about 25 weight percent ofthe phosphorous-containing additive. Flame retardance may also beimparted to the compositions by the inclusion of brominatedthermosetting resins, for example a brominated poly (epoxide), or apoly(arylene ether) having a phosphorous-containing moiety in itsbackbone.

[0063] Other art-known modifiers, fillers, antioxidants, UV absorbers,stabilizers, lubricants, plasticizers, pigments, dyes, colorants,anti-static agents, mold release agents, and flame retardants may alsobe used in the present invention such as those described in R. Gachterand H. Muller (eds.), P. P. Klemchuck (assoc. ed.), “Plastic AdditivesHandbook, 4^(th) Edition”, Hansen Publishers, (1993).

[0064] Fillers may also be added optionally to the adhesive compositionsto modify product characteristics. Suitable fillers include but are notlimited to silicates, titanium dioxide, fibers, glass fibers (includingcontinuous and chopped fibers), carbon black, graphite, calciumcarbonate, talc, and mica. Preferred conductive fillers includevapor-grown carbon fibers, such as those having an average diameter ofabout 3.5 to about 500 nanometers as described in, for example, U.S.Pat. Nos. 4,565,684 and 5,024,818 to Tibbetts et al.; 4,572,813 toArakawa; 4,663,230 and 5,165,909 to Tennent; 4,816,289 to Komatsu etal.; 4,876,078 to Arakawa et al.; 5,589,152 to Tennent et al.; and5,591,382 to Nahass et al. Suitable filler types and amounts aredictated by the desired end application and may be determined withoutundue experimentation.

[0065] The preparation of the curable resin composition may be achievedby merely blending the components under conditions suitable for theformation of an intimate blend. During mixing, the blend is preferablysufficiently heated such that the components are in solution, therebyenabling intimate mixing. Such conditions include mixing components in avessel capable of heating and shearing action to thoroughly dissolve andblend all components.

[0066] In one embodiment, the composition is prepared using a thermosetresin in its liquified (i.e., melted) state as a solvent. No additionalsolvents are employed. In this embodiment, a compatibilizer, apoly(arylene ether), and, optionally, a plasticizer, are dissolved inthe thermoset resin with heating. Depending on the cure agent employed,the cure agent may be added immediately or after cooling the solution toa temperature low enough to prevent premature curing. For example,addition of the cure agent MDEA is preferably conducted after coolingthe solution to a temperature up to about 100° C., preferably atemperature up to about 90° C. Depending on the molecular weight anddegree of functionalization of the poly(arylene ether), such cooling maybe accompanied by conversion of the solution to a fine dispersion. Theparticles in the dispersion may have particle sizes up to about 1millimeter, more commonly up to about 100 microns. Addition of the cureagent, such as, for example, MDEA or DETDA, typically creates ahomogeneous solution.

[0067] In one embodiment, at least 50 weight percent, preferably atleast 90 weight percent, of the total poly(arylene ether) is supplied tothe composition as a solid concentrate further comprising thethermosetting resin. This method is very convenient because poly(aryleneether) provided as such a solid concentrate dissolves much more easilyin thermosetting resin than does pure poly(arylene ether). In thisembodiment, the polyarylene ether and thermosetting resin are dissolvedin a suitable solvent, with heating as needed. Suitable solvents mayinclude alcohols, ketones, aliphatic hydrocarbons, aromatichydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters,amides, mixed ether-esters, sulfoxides, mixtures comprising at lease oneof the foregoing solvents, and the like. Preferred solvents includearomatic hydrocarbons, such as benzene, toluene, and xylenes, andtoluene is highly preferred. The solvent is then substantially removed(i.e., at least about 90 weight percent, preferably at least about 95weight percent, more preferably at least about 99 weight percent of thesolvent is removed) to form a powdered solid concentrate. For example,when the thermosetting resin is the epoxy EPON® 828, and thepoly(arylene ether) is a directly isolated or redistributed poly(aryleneether) having an intrinsic viscosity of about 0.30 dL/g, the solidconcentrate may comprise about 30 to about 86 weight percentpoly(arylene ether), about 10 to about 70 weight percent epoxy resin,and about 4 to about 8 weight percent compatibilizing agent, based onthe total weight of the solid concentrate. When the epoxy resin contentof the solid concentrate exceeds about 70 weight percent, the solidconcentrate may become sticky and difficult to handle. When thepoly(arylene ether) content of the solid concentrate is less than about30 weight percent, the concentrate becomes an inefficient means ofdelivering the poly(arylene ether). A preferred solid concentrate maycomprise about 30 to about 76 weight percent poly(arylene ether), about20 to about 70 weight percent thermosetting resin, and about 4 to about6 weight percent compatibilizing agent, based on the total weight of thesolid concentrate. Additional components may conveniently be added tothe solid concentrate by dry blending.

[0068] Preparation of the poly(arylene ether)-containing solidconcentrates may further include reducing the intrinsic viscosity(reducing the molecular weight) of the poly (arylene ether) via aredistribution reaction, as described above. Redistribution reactionsmay be used, for example, to convert a poly(arylene ether) having anintrinsic viscosity of at least about 0.40 dL/g to a poly(aryiene ether)having an intrinsic viscosity up to about 0.35 dL/g, preferably up toabout 0.30 dL/g.

[0069] The above described compositions and methods are useful toincrease the ductility and toughness of cured resins. The compositionmay be used to form articles by techniques including pultrusion,casting, and resin transfer molding.

[0070] The invention is further illustrated by the followingnon-limiting examples.

COMPARATIVE EXAMPLE 1

[0071] This comparative example illustrates the preparation andproperties of a composition comprising an epoxy resin and cure agent,but no poly(arylene ether). One hundred parts of2,2-bis(4-hydroxyphenyl)propane-epichlorohydrin copolymer, obtainedunder the trade name EPON® 828 from Shell Oil Co., were charged into aflask with stirring. After the epoxide was heated to 90° C. withcontinued stirring, 46 parts by weight of cure agentmethylene-bis-diethylaniline (4,4″-methylenebis(2,6-diethylaniline);MDEA; CAS Registry No. 13680-35-8; obtained as ETHACURE® 208 from EthylCorporation) was added. The resulting homogeneous solution was pouredinto open bar molds, and cured for about 2 hours at 100° C. and 4 hoursat 175° C. Molded parts were evaluated for Z-axis expansion (30° C.-260°C.; according to ASTM D6341) and K₁ C fracture toughness (according toASTM D5045). The composition and properties are summarized in the Tablebelow.

EXAMPLES 1 AND 2

[0072] These examples illustrate preparation of compositions comprisinga directly isolated poly(arylene ether) resin. Using proportionsspecified in the Table, epoxy resin EPON® 828 and plasticizer resorcinoldiphosphate were charged into a flask with stirring. The solution washeated and as the temperature reached about 100° C., polyvinyl butyral(poly(vinyl butyral-co-polyvinyl alcohol-co-polyvinyl acetate) having apolyvinyl butyral content of about 88%, obtained as BUTVAR® B76 fromSolutia) was added; the polyvinyl butyral appeared to dissolvecompletely as the temperature reached about 150° C. As the temperaturereached about 160° C., poly(arylene ether) (directly isolatedpoly(2,6-dimethylphenyl ether), intrinsic viscosity 0.30 dL/g at 25° C.in chloroform; prepared and isolated according to known techniques foroxidative coupling of 2,6-xylenol; see, for example, U.S. Pat. No.3,306,875 to Hay) was added. As the temperature reached about 200° C., asolution formed. As the solution was cooled to about 80° C., thehomogeneous solution became a slurry of finely dispersed particles. At80° C., MDEA was added and with it addition the slurry became asolution. Molding and property evaluation were conducted as described inComparative Example 1. Results are presented in the Table. It should benoted that it is not possible to prepare corresponding comparativeexamples lacking a compatibilizing agent. In the absence of acompatibilizing agent, cooling the poly(arylene ether)/polyepoxidesolution to 80° C. results in sudden precipitation of the poly(aryleneether) as a viscous mass, rather than formation of a slurry of finelydispersed particles.

EXAMPLE 3

[0073] This example illustrates preparation of a composition using asolid concentrate of poly(arylene ether) and epoxy resin. Fifty weightparts each of EPON® 828 and poly (arylene ether) (directly isolatedpoly(2,6-dimethylphenyl ether) having an intrinsic viscosity of 0.40dL/g as measured in chloroform at 25° C.; obtained as NORYL® 640-111from GE Plastics) and 0.5 parts Bisphenol A from Shell Chemical werecharged into a vessel containing toluene to form an approximately 40%solids solution. After stirring and heating at 95° C. for one hour, thepoly(arylene ether) was completely dissolved, and 0.677 parts 75%benzoyl peroxide stabilized with water (obtained from Catalyst Systems,Inc.) was added to redistribute the poly(phenylene ether) and lower itsintrinsic viscosity to 0.30 dL/g. The toluene was removed to yield asolid concentrate consisting of approximately equal weight parts ofpolyepoxide and redistributed poly(phenylene ether) having an intrinsicviscosity of 0.30 dL/g. This powder was used as the sole source ofpoly(arylene ether) in a thermosetting composition comprising 15 partsby weight poly(arylene ether), 80 parts by weight EPON® 828, and 5 partsby weight polyvinyl butyral. The thermosetting composition was preparedby combining 30 parts of the above solid concentrate with 65 parts EPON®828 and 5 parts polyvinyl butyral in a flask and heating at 200° C. withstirring until the powder dissolved. The resulting solution was cooledto about 80° C. yielding a fine precipitate of poly(arylene ether);addition of MDEA was accompanied by dissolution of the poly(aryleneether) precipitate and formation of a solution. Molding and propertyevaluation were conducted as described in Comparative Example 1. Resultsare presented in the Table. This example demonstrates an alternativetechnique for easily incorporating poly(arylene ether) into athermosetting resin matrix.

EXAMPLE 4

[0074] The procedure of Example 4 was followed, except that the powderedconcentrated was prepared and used as a 67:33 weight/weight ratio ofredistributed poly(arylene ether) and polyepoxide. Results are presentedin the Table. [t1] TABLE C. Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 COMPOSITIONPPE (0.301 V) — 9.5 15 — — PPE as a 50 50 — — — 15 — PPE/Epoxycomposition PPE as a 67:33 — — — — 15 PPE/Epoxy composition EPON ® 828100 85 78 65 72 EPON ® 828 a 50 50 — — — 15 — PPE/Epoxy compositionEPON ® 828 as a 67:33 — — — — 8 PPE/Epoxy composition Polyvinyl Butyral— 5.5 5 5 5 Resorcinol Diphosphate — 11 13 — 7 (pbw per 100 pbw PPE)Methylene-bis-diethyl 46 41 46 46 46 aniline (pbw per 100 pbw EPON ®828) PROPERTIES Molded part thickness 2.688 2.976 3.717 3.136 2.611 (mm)T_(g) (° C.) 137/156 145/207 142/187 141/207 145/203 Z-axis expansion,30- 3.05 3.46 3.52 3.18 3.50 260° C., neat resin bar (%) K₁C fracturetoughness 0.75 — 0.97 1.10 0.99 (MPa-m^(1′2))

[0075] The results show that Examples 1-4 provide higher fracturetoughness than Comparative Example 1.

[0076] While the invention has been described with reference to apreferred embodiment, it will be understood by those skilled in the artthat various changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing fromessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

[0077] All cited patents and other references are incorporated herein byreference.

1. A curable composition, comprising: about 5 to about 50 parts byweight of a poly(arylene ether); about 25 to 90 parts by weight of athermosetting resin selected from the group consisting of epoxy resins,polyester resins, polyimide resins, bis-maleimide resins, cyanate esterresins, vinyl resins, benzoxazine resins, benzocyclobutene resins, andmixtures comprising at least one of the foregoing thermosetting resins;about 0.5 to about 15 parts by weight of a compatibilizing agentselected from the group consisting of polyvinyl acetal resins,styrene-butadiene-styrene block copolymers, styrene-ethylene-styreneblock copolymers, styrene-ethylene-butylene-styrene block copolymers,functionalized butadiene-acrylonitrile copolymers, styrene-butadienecore shell rubbers, styrene-butadiene-styrene core shell rubbers, andmixtures comprising at least one of the foregoing compatibilizingagents; and about 3 to about 150 parts by weight per 100 parts of weightof the thermosetting resin of an amine cure agent selected from thegroup consisting of amidoamines, polyamides, cycloaliphatic amines,modified cycloaliphatic amines, aromatic amines, modified aromaticamines, BF₃-amine adducts, imidazoles, guanidines, arylene polyamines,and mixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to
 100. 2. Thecomposition of claim 1, wherein the poly(arylene ether) comprises aplurality of structural units of the formula

wherein for each structural unit, each Q¹ is independently halogen,primary or secondary C₁-C₇ alkyl, phenyl, C₁-C₇ haloalkyl, C₁-C₇aminoalkyl, C₁-C₇ hydrocarbonoxy, or C₂-C₇ halohydrocarbonoxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; and eachQ² is independently hydrogen, halogen, primary or secondary C₁-C₇ alkyl,phenyl, C₁-C₇ haloalkyl, C₁-C₇ aminoalkyl, C₁-C₇ hydrocarbonoxy, orC₂-C₇ halohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms.
 3. The composition of claim 2 wherein each Q¹is independently C₁-C₇ alkyl, and each Q² is hydrogen.
 4. Thecomposition of claim 3 wherein the poly(arylene ether) is a homopolymercomprising 2,6-dimethylphenylene ether units, or a random copolymercomprising 2,6-dimethylphenylene ether units in combination with2,3,6-trimethyl-1,4-phenylene ether units.
 5. The composition of claim1, wherein the poly(arylene ether) comprises a directly isolatedpoly(arylene ether).
 6. The composition of claim 1, wherein thepoly(arylene ether) comprises a redistributed poly(arylene ether). 7.The composition of claim 1, wherein the poly(arylene ether) has anintrinsic viscosity of about 0.20 dL/g to about 0.40 dL/g as measured at25° C. in chloroform.
 8. The composition of claim 1, comprising about 10to about 40 parts by weight of the poly(arylene ether) per 100 parts byweight total of the poly(arylene ether), the thermosetting resin, andthe compatibilizing agent.
 9. The composition of claim 1, wherein thethermosetting resin comprises an epoxy resin.
 10. The composition ofclaim 1, wherein the thermosetting resin comprises a reaction product of2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin.
 11. The compositionof claim 1, comprising about 50 to about 85 parts by weight of thethermosetting resin per 100 parts by weight total of the poly (aryleneether), the thermosetting resin, and the compatibilizing agent.
 12. Thecomposition of claim 1, wherein the compatibilizing agent comprises apolyvinyl acetal.
 13. The composition of claim 1, wherein thecompatibilizing agent comprises a polyvinyl butyral.
 14. The compositionof claim 1, comprising about 2 to about 10 parts by weight of thecompatibilizing agent per 100 parts by weight total of the poly(aryleneether), the thermosetting resin, and the compatibilizing agent.
 15. Thecomposition of claim 1, wherein the cure agent comprises an arylenepolyamine.
 16. The composition of claim 1, wherein the cure agentcomprises 4,4-methylenebis(2,6-diethylanilin.e).
 17. The composition ofclaim 1, comprising about 20 to about 100 parts by weight of the cureagent per 100 parts by weight of the thermosetting resin.
 18. Thecomposition of claim 1, further comprising about 0.1 to about 20 partsby weight per 100 parts by weight poly(arylene ether) of a plasticizereffective for poly(arylene ether) resins.
 19. The composition of claim18, wherein the plasticizer is selected from the group consisting ofresorcinol diphosphate, bisphenol-A-diphosphate, isopropylated phenolphosphate, and mixtures comprising at least one of the foregoingplasticizers.
 20. The composition of claim 1, further comprising anadditive selected from the group consisting of fillers, antioxidants, UVabsorbers, thermal stabilizers, light stabilizers, pigments, dyes,colorants, anti-static agents, flame retardants, impact modifiers, moldrelease agents, and mixtures comprising at least one of the foregoingadditives.
 21. The curable resin composition of claim 1, wherein theresin composition is substantially free of solvent.
 22. A curablecomposition, comprising: about 10 to about 40 parts by weight of apoly(arylene ether) having an intrinsic viscosity of about 0.20 dL/g toabout 0.40 dL/g as measured at 25° C. in chloroform; about 50 to about85 parts by weight of an epoxy resin; about 2 to about 10 parts byweight of a polyvinyl butyral; and about 20 to about 100 parts by weightper 100 parts of weight of the thermosetting resin of an aromatic aminecure agent; wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to
 100. 23. Amethod of forming a curable resin composition, comprising: forming anintimate blend comprising about 5 to about 50 parts by weight of apoly(arylene ether); about 25 to 90 parts by weight of a thermosettingresin selected from the group consisting of epoxy resins, polyesterresins, polyimide resins, bis-maleimide resins, cyanate ester resins,vinyl resins, benzoxazine resins, benzocyclobutene resins, and mixturescomprising at least one of the foregoing thermosetting resins; about 0.5to about 15 parts by weight of a compatibilizing agent selected from thegroup consisting of polyvinyl acetal resins, styrene-butadiene-styreneblock copolymers, styrene-ethylene-styrene block copolymers,styrene-ethylene-butylene-styrene block copolymers, functionalizedbutadiene-acrylonitrile copolymers, styrene-butadiene core shellrubbers, styrene-butadiene-styrene core shell rubbers, and mixturescomprising at least one of the foregoing compatibilizing agents; andabout 3 to about 150 parts by weight per 100 parts by weightthermosetting resin of an amine cure agent selected from the groupconsisting of amidoamines, polyamides, cycloaliphatic amines, modifiedcycloaliphatic amines, aromatic amines, modified aromatic amines,BF₃-amine adducts, imidazoles, guanidines, arylene polyamines, andmixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to
 100. 24. Themethod of claim 23, wherein at least about 50 weight percent of thetotal poly(arylene ether) is provided in the form of a solid concentratecomprising about 30 weight percent to about 90 weight percentpoly(arylene ether), and about 10 weight percent to about 70 weightpercent thermosetting resin, wherein the weight percents are based onthe total weight of the solid concentrate.
 25. The method of claim 24,wherein forming an intimate blend comprises heating the poly(aryleneether), the thermosetting resin, and the compatibilizing agent to atemperature up to about 100° C.
 26. A method of forming a curable resincomposition, comprising: forming a first intimate blend comprising about5 to about 50 parts by weight of a poly(arylene ether); about 25 to 90parts by weight of a thermosetting resin selected from the groupconsisting of epoxy resins, polyester resins, polyimide resins,bis-maleimide resins, cyanate ester resins, vinyl resins, benzoxazineresins, benzocyclobutene resins, and mixtures comprising at least one ofthe foregoing thermosetting resins; and about 0.5 to about 15 parts byweight of a compatibilizing agent selected from the group consisting ofpolyvinyl acetal resins, styrene-butadiene-styrene block copolymers,styrene-ethylene-styrene block copolymers,styrene-ethylene-butylene-styrene block copolymers, functionalizedbutadiene-acrylonitrile copolymers, styrene-butadiene core shellrubbers, styrene-butadiene-styrene core shell rubbers, and mixturescomprising at least one of the foregoing compatibilizing agents; andforming a second intimate blend comprising the first intimate blend andabout 3 to about 150 parts by weight per 100 parts by weightthermosetting resin of an amine cure agent selected from the groupconsisting of amidoamines, polyamides, cycloaliphatic amines, modifiedcycloaliphatic amines, aromatic amines, modified aromatic amines,BF₃-amine adducts, imidazoles, guanidines, arylene polyamines, andmixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to
 100. 27. Themethod of claim 26, wherein forming the first intimate blend comprisesheating the poly(arylene ether), the thermosetting resin, and thecompatibilizing agent to a temperature of at least about 150° C. to forma homogeneous solution.
 28. The method of claim 27, wherein forming thefirst intimate blend further comprises cooling the homogeneous solutionto a temperature up to about 100° C. to form a slurry of solidparticles, wherein the solid particles have an average particle size upto about 1 millimeter.
 29. A method of forming a poly(aryleneether)-containing solid concentrate, comprising: blending about 30 toabout 90 parts by weight of a poly(arylene ether) and about 10 to about70 parts by weight of a thermosetting resin in the presence of asuitable solvent to form a homogeneous solution; and substantiallyremoving the suitable solvent to yield a solid concentrate; wherein theparts by weight of the poly(arylene ether) and the thermosetting resinsum to
 100. 30. The method of claim 29, wherein the suitable solvent isselected from the group consisting of alcohols, ketones, aliphatichydrocarbons, aromatic hydrocarbons, chlorohydrocarbons,nitrohydrocarbons, ethers, esters, amides, mixed ether-esters,sulfoxides, and mixtures comprising at least one of the foregoingsolvents.
 31. The method of claim 29, further comprising redistributingthe poly(arylene ether) in the presence of a phenolic compound and anoxidizing agent to form a redistributed poly(arylene ether) having anintrinsic viscosity up to about 0.35 dL/g as measured at 25° C. inchloroform.
 32. A method of forming a poly(arylene ether)-containingsolid concentrate, comprising: blending about 30 to about 90 parts byweight of a poly(arylene ether), about 10 to about 70 parts by weight ofa thermosetting resin, and about 3 to about 150 parts by weight of acure agent in the presence of a suitable solvent to form a homogeneoussolution; and removing the suitable solvent to yield a solidconcentrate; wherein the parts by weight of the poly(arylene ether) andthe thermosetting resin sum to 100; and wherein the parts by weight ofthe cure agent are based on 100 parts by weight of the thermosettingresin.
 33. A curable resin composition prepared according to the methodof claim
 23. 34. A curable resin composition prepared according to themethod of claim
 24. 35. A curable resin composition prepared accordingto the method of claim
 25. 36. A poly(arylene ether)-containing solidconcentrate prepared according to the method of claim
 29. 37. Apoly(arylene ether)-containing solid concentrate prepared according tothe method of claim
 32. 38. A cured composition comprising the reactionproduct of: about 5 to about 50 parts by weight of a poly(aryleneether); about 25 to 90 parts by weight of a thermosetting resin selectedfrom the group consisting of epoxy resins, polyester resins, polyimideresins, bis-maleimide resins, cyanate ester resins, vinyl resins,benzoxazine resins, benzocyclobutene resins, and mixtures comprising atleast one of the foregoing thermosetting resins; about 0.5 to about 15parts by weight of a compatibilizing agent selected from the groupconsisting of polyvinyl acetal resins, styrene-butadiene-styrene blockcopolymers, styrene-ethylene-styrene block copolymers,styrene-ethylene-butylene-styrene block copolymers, functionalizedbutadiene-acrylonitrile copolymers, styrene-butadiene core shellrubbers, styrene-butadiene-styrene core shell rubbers, and mixturescomprising at least one of the foregoing compatibilizing agents; andabout 3 to about 150 parts by weight per 100 parts of weight of thethermosetting resin of an amine cure agent selected from the groupconsisting of amidoamines, polyamides, cycloaliphatic amines, modifiedcycloaliphatic amines, aromatic amines, modified aromatic amines,BF₃-amine adducts, imidazoles, guanidines, arylene polyamines, andmixtures comprising at least one of the foregoing amine cure agents;wherein the parts by weight of the poly(arylene ether), thethermosetting resin, and the compatibilizing agent sum to
 100. 39. Anarticle comprising the cured resin composition of claim 38.